Materials that can be structured, method for producing the same and their use

ABSTRACT

The invention provides low molecular weight or polymeric organic materials in which at least one hydrogen atom is replaced by a group of the formula (A) 
                         
where R is alkyl group, alkoxyalkyl group, alkoxy group, thioalkoxy group, aryl group or alkenyl group, in each of which one or more hydrogen atoms may be replaced and one or more nonadjacent carbon atoms may be replaced.
         Z is —O—, —S—, —CO—, —COO—, —O—CO— or a bivalent group —(CR 1 R 2 ) n — in which R 1  and R 2  are hydrogen, alkyl, alkoxy, alkoxyalkyl or thioalkoxy group, aryl or alkenyl, in each of which one or more hydrogen atoms may be replaced and one or more nonadjacent carbon atoms may be replaced, and n is an integer from 1 to 20.   X is a bivalent group —(CR 1 R 2 ) n — and, with the proviso that the number of these A groups is limited by the maximum number of available substitutable hydrogen atoms. The invention also relates to their use for producing optionally multilayered structured light emitting diodes, lasers, solar cells, waveguides or integrated circuits.

For a few years, there has existed a rapidly growing needs for organicmaterials which are required for use in electronic applications. Typicalapplications are those in organic (OLED) or polymeric light emittingdiodes (PLED) (cf., for example, EP-A-0 676 461, WO 98/27136), organicsolar cells (cf., for example, WO 98/48433, WO 94/05045), organic lasers(for example WO 98/03566) and also in organic circuits (ICs) (forexample WO 95/31833, WO 99/10939).

The use of materials is described [lacuna] the abovementionedapplications and patents and the references cited therein and will notbe further reinforced here. With regard to the use, these texts areincorporated in the present invention by way of reference.

Compounds used in the abovementioned fields of application are both lowmolecular weight and polymeric compounds.

For organic and polymeric light emitting diodes and laser applications,these include both active materials (i.e. light emitting substances) andmaterials for further auxiliary layers, i.e., for example, chargetransport layers having certain optical properties.

For use in the fields of application of solar cells and organicswitching elements, there is a preference and a requirement for organicsemiconductors and insulators, and therefore in general for chargetransport materials having different transport properties.

In all of these applications, typically used compounds in the spectrumof high molecular weight compounds are conjugated or at least partiallyconjugated polymers. Typical representatives of conjugated polymers arepoly(p-phenylene-vinylene) [PPV] or poly-p-phenylene [PPP]. When the PPPstructure is composed predominantly of fluorene building blocks, thesematerials are also referred to as polyfluorenes. When the PPP structurepredominantly contains spiro-9,9′-bifluorene units, these are known aspolyspiros.

For the purposes of this invention, partially conjugated polymers arethose substances which either have mainly conjugated segments in themain chain which are interrupted by nonconjugated segments, or are thosewhich have relatively long conjugated segments in the side chain.

On the other hand, low molecular weight compounds are alreadysuccessfully used in some of the abovementioned fields of application.

Among the low molecular weight compounds, those having aromaticπ-systems (aromatics) have gained particular importance. In addition to2-dimensional aromatics, for example triphenylene derivatives(DE-A-4422332), aromatics having a 3-dimensional spatially extendedstructure in particular have proven advantageous. Typicalrepresentatives are compounds which are based on spirobifluorene(EP-A-676461), triptycene or iptycene (DE-A-19744792).

Although different types of substance already find use in all of theseapplications, the development of these types of compound should in noway be regarded as being complete.

For instance, there is firstly a strong pressure to lengthen theoperating lifetime of the compounds in the respective applications, andsecondly structuring in certain applications is also an unsolvedproblem.

Depending on the field of use, structuring is a very importantcriterion: in displays (based on OLED or PLED technology), for example,the individual pixels have to be generated. Of course, a similar problemalso presents itself in generating organic circuits and sometimes alsoin structuring organic solar cell panels or laser arrays. Customarily,these structurings are carried out at the “feeds”, i.e., for example, atthe electrodes. This may be effected, for example, using shadow masks ofthe template type; however, for industrial mass production this mayresult in distinct disadvantages: after being used once or more thanonce, the masks are unusable owing to deposit formation and have to beregenerated in a costly and inconvenient manner.

A further possibility for structuring also involves applying the activelayer (here: either the light-emitting layer in OLEDs/PLEDs and lasersor charge transport layers in all applications) directly in structuredform. Since this presents considerable problems is understandable fromthe dimensions alone: structures in the range from a few tens of μm haveto be generated at layer thicknesses in the range from approx. 100 nm toa few μm. Printing processes (such as offset printing, inkjet printing,or similar techniques) may possibly be suitable for this purpose,although no such process is yet suitable for production. In this casealso (in the field of OLEDs), the mask technology already outlined abovefor the electrodes is used. However, this is clearly accompanied in thiscase by the above-outlined problems of deposit formation.

Polym. Materials, Science and Engineering 80, 122 (1999) disclosesN,N,N′,N′-tetraphenylbenzidines functionalized by oxetane groups whosecrosslinking can be photoinduced. The abovementioned class of compoundsare used as structurable hole conductors in organic light emittingdiodes (OLEDs), so that structured OLEDs can be obtained.

It is therefore an object of the present invention to providestructurable materials which are suitable for use in structured devices,such as OLEDs, PLEDs, organic lasers, organic switching elements andorganic solar cells, and result in the property profile of these devicesat least being retained.

It has now been found that, surprisingly, organic materials can bestructured in the above-listed applications when they contain at leastone oxetane group capable of crosslinking whose crosslinking reactioncan be initiated and controlled in a targeted manner. This may becarried out under suitable conditions in such a way that no impairmentof the other device characteristics occurs, but so that the structuringis distinctly simplified or is made possible in the first place.

The invention therefore provides low molecular weight or polymericorganic materials which are used in the abovementioned electronicapplications, in which at least one hydrogen atom is replaced by a groupof the formula (A)

where

-   R is a straight-chain, branched or cyclic alkyl, alkoxyalkyl, alkoxy    or thioalkoxy group having from 1 to 20 carbon atoms, C₄-C₁₈-aryl or    C₂-C₁₀-alkenyl, in each of which one or more hydrogen atoms may be    replaced by halogen, such as Cl or F, or CN, and one or more    nonadjacent carbon atoms may be replaced by —O—, —S—, —CO—, —COO— or    —O—CO—,-   Z is —O—, —S—, —CO—, —COO—, —O—CO— or a bivalent group —(CR₁R₂)_(n)—    in which R₁ and R₂ are each independently hydrogen, a    straight-chain, branched or cyclic alkyl, alkoxy, alkoxyalkyl or    thioalkoxy group having from 1 to 20 carbon atoms, C₄-C₁₈-aryl or    C₂-C₁₀-alkenyl, in each of which one or more hydrogen atoms may be    replaced by halogen, such as Cl or F, or CN, and one or more    nonadjacent carbon atoms may be replaced by —O—, —S—, —CO—, —COO— or    —O—CO—,-   X is a bivalent group —(CR₁R₂)_(n)— in which R₁ and R₂ are each    independently hydrogen, a straight-chain, branched- or cyclic alkyl,    alkoxy, alkoxyalkyl- or thioalkoxy group having from 1 to 20 carbon    atoms, C₄-C₁₈-aryl or C₂-C₁₀-alkenyl, in each of which one or more    hydrogen atoms may be replaced by halogen, such as Cl or F, or CN,    and-   n is an integer from 1 to 20, preferably from 3 to 10, in particular    3 or 6, with the proviso that the number of these A groups is    limited by the maximum number of available, i.e. substitutable,    hydrogen atom.

DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the device data for crosslinked and uncrosslinkedpolymer P1 according to the invention.

FIG. 2 illustrates the profile obtained using a profilmeter.

The electronics materials according to the invention areelectroluminescent or laser materials such as

-   A) homo- or copolymers based on PPV or polyfluorenes or polyspiro-   B) low molecular weight compounds having a 3-dimensional    spirobifluorene structure,-   C) low molecular weight compounds having a 3-dimensional triptycene    structure-   D) low molecular weight compounds having a 2-dimensional    triphenylene structure-   E) derivatives of perylenetetracarboxylic diimide-   F) derivatives of quinaciridone-   G) organic lanthanide complexes-   H) derivatives of aluminum tris-quinoxalinate-   I) oxadiazole derivatives    or hole conductors such as-   J) polystyrenes, polyacrylates, polyamides or polyesters which bear    derivatives of tetraarylbenzidine in the side chain,-   K) low molecular weight compounds having a 2-dimensional    triphenylene structure or electron conductors such as-   L) derivatives of aluminum tris-quinoxalinate-   M) oxadiazole derivatives.

The oxetane content is defined by the molar ratio of oxetane rings basedon all organic rings, i.e. including the oxetane rings, in theparticular structure. This can generally be determined by analyticalmethods. In addition to IR spectroscopy, one of the preferred methods isnuclear magnetic resonance spectroscopy (NMR).

For the purposes of the invention, rings are cyclic structural-elementsformed from at least three ring atoms with the proviso that at least twocarbon atoms are present (The Ring Index, Patterson and Capell, ReinholdPublishing Company, 1940 and Handbook of Chemistry and Physics, 62^(nd)ed. 1981, C-48).

The oxetane content may be varied within wide ranges of from 0.01 to0.6. In the lower range, low degrees of cross-linking are achieved whichresult in relatively soft, rubber-elastic to gel-like layers. In theupper range, high crosslinking densities are achieved havingthermoset-like properties, for example Bakelite.

A1) The homo- and copolymers of PPV contain one or more structural unitsof the formula (B), where at least one hydrogen atom in the polymer isreplaced by a substituent of the formula (A).

-   The substituents R′ to R″″″ are the same or different and are each    H, CN, F, Cl or a straight-chain, branched or cyclic alkyl or alkoxy    group having from 1 to 20 carbon atoms where one or more nonadjacent    CH₂ groups may be replaced by —O—, —S—, —CO—, —COO—, —O—CO—, —NR¹—,    —(NR²R³)⁺—A⁻, or —CONR⁴—, and where one or more hydrogen atoms may    be replaced by F, or an aryl group having from 4 to 14 carbon atoms    which may be substituted by one or more nonaromatic radicals R′.-   R₁, R₂, R₃, R₄ are the same or different and are each aliphatic or    aromatic hydrocarbon radicals having from 1 to 20 carbon atoms or    else hydrogen.-   A—: is a singly charged anion or its equivalent.

Preference is given to PPVs according to WO 98/27136, which arerepresented in formula (C)

where the symbols and indices are defined as follows:

-   Aryl: is an aryl group having from 4 to 14 carbon atoms;-   R′, R″: are the same or different and are each a straight-chain or    branched or cyclic alkyl or alkoxy group having from 1 to 20 carbon    atoms where one or more nonadjacent CH₂ groups may be replaced by    —O—, —S—, —CO—, —COO—, —O—CO—, —NR¹—, —(NR²R³)⁺—A⁻, or —CONR⁴—, and    where one or more hydrogen atoms may be replaced by F, or are CN, F,    Cl or an aryl groups having from 4 to 14 carbon atoms which may be    substituted by one or more nonaromatic radicals R′;-   R¹, R², R³, R⁴ are the same or different and are each aliphatic or    aromatic hydrocarbon radicals having from 1 to 20 carbon atoms or    else H.-   A⁻: is a singly charged anion or its equivalent;-   m: is 0, 1 or 2;-   n: is 1, 2, 3, 4 or 5.

Particular preference is given to polymers consisting mainly ofrepeating units of the formula (C).

Very particular preference is also given to copolymers consistingsubstantially of, more preferably consisting of, repeating units of theformula (I) and further repeating units which preferably likewisecontain poly(arylenevinylene) structures, more preferably2,5-dialkoxy-1,4-phenylenevinylene structures, where the alkoxy groupsare preferably straight-chain or branched and contain from 1 to 22carbon atoms.

For the purposes of the invention, copolymers comprise random,alternating, regular and also block structures.

Preference is likewise given to polymers containing repeating units ofthe formula (C) in which the symbols and indices are defined as follows:

-   Aryl is phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl, 2-, 3- or    4-pyridinyl, 2-, 4- or 5-pyrimidinyl, 2-pyrazinyl, 3- or    4-pyridazinyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline, 2- or    3-thiophenyl, 2- or 3-pyrrolyl, 2- or 3-furanyl or    2-(1,3,4-oxadiazol)yl;-   R′ is in each case the same or different and is CN, F, Cl, CF₃ or a    straight-chain or branched alkoxy group having from 1 to 12 carbon    atoms;-   R″ is in each case the same or different and is a straight-chain or    branched alkyl or alkoxy group having from 1 to 12 carbon atoms;-   n is 0, 1, 2 or 3, more preferably 0, 1 or 2.

The preparation of such polymers is described in detail in WO 98/27136.Corresponding polymers according to the invention may be prepared bycopolymerizing appropriate monomers which contain the oxetane group ofthe formula (A).

A2) The homo- and copolymers of polyfluorene contain one or morestructural units of the formula (D), where at least one hydrogen atom inthe polymer is replaced by a substituent of the formula (A).

The substituents R′ to R″″ are the same or different and are H, CN, F,Cl or a straight-chain, branched or cyclic alkyl or alkoxy group havingfrom 1 to 20 carbon atoms where one or more nonadjacent CH₂ groups maybe replaced by —O—, —S—, —CO—, —COO—, —O—CO—, —NR¹—, —(NR²R³)⁺—A⁻, or—CONR⁴—, and where one or more hydrogen atoms may be replaced by F, oran aryl group having from 4 to 14 carbon atoms which may be substitutedby one or more nonaromatic radicals R′.

-   R¹, R², R³, R⁴ are the same or different and are each aliphatic or    aromatic hydrocarbon radicals having from 1 to 20 carbon atoms or    else hydrogen.-   A⁻: is a singly charged anion or its equivalent;-   n, m: are each 0, 1, 2 or 3, preferably 0 or 1.

A2.1) Preference is given to structures according to DE-A-19846767 whichare detailed hereinbelow. In addition to structural units of the formula(E1)

where

-   R¹, R² are the same or different and are each hydrogen,    C₁-C₂₂-alkyl, C₂-C₂₀-heteroaryl, C₅-C₂₀-aryl, F, Cl or CN; where the    abovementioned alkyl radicals may be branched or unbranched or else    be cycloalkyls, and individual, nonadjacent CH₂ groups of the alkyl    radical may be replaced by O, S, C═O, COO, N—R⁵ or else C₂-C₁₀-aryls    or heteroaryls, where the abovementioned aryls/heteroaryls may be    substituted by one or more nonaromatic substituents R³. Preference    is given to compounds in which R¹ and R² are both the same and are    not hydrogen or chlorine; preference is further given to compounds    in which R¹ and R² are different and are also not hydrogen;-   R³, R⁴ are the same or different and are each H, C₁-C₂₂-alkyl,    C₂-C₂₀-heteroaryl, C₅-C₂₀-aryl, F, Cl, CN, SO₃R⁵ or NR⁵R⁶; the alkyl    radicals may be branched or unbranched or else be cycloalkyls; and    individual, nonadjacent CH₂ groups of the alkyl radical may be    replaced by O, S, C═O, COO, N—R⁵ or C₂-C₁₀-aryls or heteroaryls,    where the abovementioned aryls/heteroaryls may be substituted by one    or more nonaromatic substituents R³,-   R⁵, R⁶ are the same or different and are each hydrogen,    C₁-C₂₂-alkyl, C₂-C₂₀-heteroaryl or C₅-C₂₀-aryl; the alkyl radicals    may be branched or unbranched or else be cycloalkyls; and    individual, nonadjacent CH₂ groups of the alkyl radical may be    replaced by O, S, C═O, COO, N R⁵ or else C₂ C₁₀ aryls, where the    abovementioned aryls may be substituted by one or more nonaromatic    substituents R³, and-   m, n are each an integer 0, 1, 2 or 3, preferably 0 or 1,    these polymers contain structural units of the formula (E2)

where

-   Ar¹, Ar² are each mono- or polycyclic aromatic conjugated systems    having from 2 to 40 carbon atoms in which one or more carbon atoms    may be replaced by nitrogen, oxygen or sulfur, and which may be    substituted by one or more substituents R³. It is entirely possible    or sometimes even preferred that the aromatics Ar¹ and Ar² are    bonded to each other via a bond or a further substituted or    unsubstituted carbon atom or heteroatom and thus form a common ring.-   R⁷ is in each case the same or different and is C₁-C₂₂-alkyl,    C₂-C₂₀-heteroaryls or C₅-C₂₀-aryl; the alkyl radicals may be    branched or unbranched or else be cycloalkyls; and individual,    nonadjacent CH₂ groups of the alkyl radical may be replaced by O, S,    C═O, COO, N—R⁵ or else simple aryls, where the abovementioned    aryls/heteroaryls may be substituted by one or more nonaromatic    substituents R³.

Very particular preference is given to the structural units of theformula (E2) being derived from the following basic units:

-   -   diphenylamine derivatives which are incorporated into the        polymer in the 4,4′-position;    -   phenothiazine or phenoxazine derivatives which are incorporated        into the polymer in the 3,7-position;    -   carbazole derivatives which are incorporated into the polymer in        the 3,6-position;    -   dihydrophenazine derivatives which are incorporated into the        polymer in the 2,6- or 2,7-position;    -   dihydroaciridine derivatives which are incorporated into the        polymer in the 3,7-position.

A2.2) Preference is likewise given to structures according toDE-A-19846766 which are detailed hereinbelow. These polymers containstructural units of the formula (F)

where

-   R¹, R² are two different substituents from the group of C₂-C₄₀-aryl    or heteroaryl; where the abovementioned aryls or heteroaryls may be    substituted by one or more substituents R³; for the purposes of this    invention, the aryls and heteroaryls are of different types when    they differ in the type or arrangement of substituents,-   R³, R⁴ are the same or different and are each C₁-C₂₂-alkyl,    C₂-C₂₀-aryl, F, Cl, CN, SO₃R⁵ or NR⁵R⁶; the alkyl radicals may be    branched or unbranched or else be cycloalkyls; and individual,    nonadjacent CH₂ groups of the alkyl radical may be replaced by O, S,    C═O, COO, N—R⁵ or else simple aryls, where the abovementioned aryls    may be substituted by one or more nonaromatic substituents R³,-   R⁵, R⁶ are the same or different and are each H, C₁-C₂₂-alkyl or    C₂-C₂₀-aryl; the alkyl radicals may be branched or unbranched or    else be cycloalkyls; and individual, nonadjacent CH₂ groups of the    alkyl radical may be replaced by O, S, C═O, COO, N—R⁵ or else simple    aryls, where the abovementioned aryls may be substituted by one or    more nonaromatic substituents R³, and-   m, n are each an integer 0, 1, 2 or 3, preferably 0 or 1.

Very particular preference is given to R¹, R² being two differentsubstituents from the group of C₅-C₄₀-aryl and C₂-C₄₀-heteroaryl; wherethe abovementioned aryls and heteroaryls may be substituted by one ormore R³ substituents.

A2.3) Preference is likewise given to structures according to DE19846768.0 which are detailed hereinbelow. These are polyfluoreneswhich, in addition to units of the formula (E1)

where

-   R¹, R² are the same or different and are each hydrogen,    C₁-C₂₂-alkyl, C₂-C₂₀-aryl or -heteroaryl, F, Cl or CN; where the    abovementioned alkyl radicals may be branched or unbranched or else    be cycloalkyls, and individual, nonadjacent CH₂ groups of the alkyl    radical may be replaced by O, S, C═O, COO, N—R⁵ or else simple    aryls, where the abovementioned aryls may be substituted by one or    more substituents R³. Preference is given to compounds in which R¹    and R² are both the same and are not hydrogen or chlorine;    preference is further given to compounds in which R¹ and R² are    different and are also not hydrogen;-   R³, R⁴ are the same or different and are each, C₁-C₂₂-alkyl,    C₂-C₂₀-aryl or -heteroaryl, F, Cl, CN, SO₃R⁵ or NR⁵R⁶; the alkyl    radicals may be branched or unbranched or else be cycloalkyls; and    individual, nonadjacent CH₂ groups of the alkyl radical may be    replaced by O, S, C═O, COO, N—R⁵ or else simple aryls, where the    abovementioned aryls may be substituted by one or more nonaromatic    substituents R³,-   R⁵, R⁶ are the same or different and are each hydrogen,    C₁-C₂₂-alkyl, or C₂-C₂₀-aryl; the alkyl radicals may be branched or    unbranched or else be cycloalkyls; and individual, nonadjacent CH₂    groups of the alkyl radical may be replaced by O, S, C═O, COO, N—R⁵    or else simple aryls, where the abovementioned aryls may be    substituted by one or more nonaromatic substituents R³, and-   m, n are each an integer 0, 1, 2 or 3, preferably 0 or 1,    always also contain structural units of the formula (G1)*

where

-   Aromatic is a mono- or polycyclic aromatic conjugated system having    from 5 to 20 carbon atoms in which one or more carbon atoms may be    replaced by nitrogen, oxygen or sulfur, and whose linking points are    chosen in such a way that an angle along the main polymer chain    unequal to 180°, preferably less than 120°, particularly preferably    less than 90° results.

In this context, particular preference is given to polymers containingat least 1 mol %, preferably from 2 mol % to 50 mol %, of structuralunits (one or more different) of the structural unit (G1).

The preparation of such polymers is described in detail inDE-A-19846767, DE-A-19846766 and DE-A-19846768. Corresponding polymersaccording to the invention may be prepared by copolymerizingcorresponding monomers which bear the oxetane group.

A3) The homo- and copolymers of the polyspiro contain one or morestructural units of the formula (H) where at least one hydrogen atom inthe polymer are replaced by a substituent of the formula (A).

The substituents R′ to R″″ are the same or different and are H, CN, F,Cl or a straight-chain, branched or cyclic alkyl or alkoxy group havingfrom 1 to 20 carbon atoms where one or more nonadjacent CH₂ groups maybe replaced by —O—, —S—, —CO—, —COO—, —O—CO—, —NR¹—, —(NR²R³)⁺—A⁻, or—CONR⁴—, and where one or more hydrogen atoms may be replaced by F, oran aryl group having from 4 to 40 carbon atoms which may be substitutedby one or more nonaromatic radicals R′.

-   R¹, R², R³, R⁴ are the same or different and are each aliphatic or    aromatic hydrocarbon radicals having from 1 to 20 carbon atoms or    else hydrogen.-   A⁻: is a singly charged anion or its equivalent;-   n, m, o, p: are each 0, 1, 2 or 3, preferably 0, 1 or 2.

Preferred embodiments of the polyspiros are contained in (U.S. Pat. No.5,621,131).

The preparation of such polymers is described in detail in U.S. Pat. No.5,621,131. Corresponding polymers according to the invention may beprepared by copolymerizing appropriate monomers which bear the oxetanegroup.

B) The low molecular weight compounds having a 3-dimensionalspirobifluorene structure consist of structural units of the formula(I1)

where the benzo groups may each independently be substituted and/orfused and where at least one hydrogen atom is replaced by a substituentof the formula (A). In this context, preference is given to usingcompounds according to EP-A-0676461, as represented in formula (I2)

where the symbols and indices are defined as follows:

K, L, M, N are the same or different and are each

-   R may in each case be the same or different and have the same    definition as K, L, M or N, or is H, a linear or branched alkyl,    alkoxy or ester group having from 1 to 22 carbon atoms, —CN, —NO₂,    —NR²R³, —Ar or —O—Ar;-   Ar is phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 2-thienyl or    2-furanyl, where each of these groups may bear one or two R    radicals,-   m, n, p, are each 0, 1, 2 or 3;-   X, Y are the same or different and are CR, N;-   Z is —O—, —S—, —NR¹—, —CR¹R⁴—, —CH═CH— or —CH═N—;-   R¹, R⁴ may be the same or different and may each have the same    definition as R-   R², R³ are the same or different and are each H, a linear or    branched alkyl group having from 1 to 22 carbon atoms, —Ar or    3-methylphenyl.

The preparation of such compounds is described in detail in EP 676461.Corresponding compounds according to the invention can be prepared byreplacing appropriate substituents or hydrogen atoms by the oxetanegroup of the formula (A).

C) The low molecular weight compounds having a 3-dimensional triptycenestructure consist of structural units of the formula (J)

where the benzo groups may each independently be substituted and/orfused and where at least one hydrogen atom is replaced by a substituentof the formula (A). Preference is given to using compounds according toDE-A-19744792. The preparation of such compounds is described in detailin DE-A-19744792. Corresponding compounds according to the invention canbe prepared by replacing appropriate substituents or hydrogen atoms bythe oxetane group of the formula (A).

D) The low molecular weight compounds having a 2-dimensionaltriphenylene structure consist of structural units of the formula (K)

where the benzo groups may each independently be substituted and/orfused and where at least one hydrogen atom is replaced by a substituentof the formula (A). Preference is given to using compounds according toDE-A-4422332. The preparation of such compounds is described in detailin DE-A-4422332. Corresponding compounds according to the invention canbe prepared by replacing appropriate substituents or hydrogen atoms bythe oxetane group of the formula (A).

E) The derivatives of the perylenetetracarboxylic diimide consist ofstructural units of the formula (L)

where the benzo groups may each independently be substituted and whereat least one hydrogen atom is replaced by a substituent of the formula(A). Similarly to R′ and R″, these substituents may be the same ordifferent and may each be a straight-chain, branched or cyclic alkyl oralkoxy group having from 1 to 20 carbon atoms where one or morenonadjacent CH₂ groups may be replaced by —O—, —S—, —CO—, —COO—, —O—CO—,—NR¹—, —(NR²R³)⁺—A⁻, or —CONR⁴—, and where one or more hydrogen atomsmay be replaced by F, or an aryl group having from 4 to 14 carbon atomswhich may be substituted by one or more nonaromatic radicals R′.Furthermore, the substituents other than R′ and R″ may also be CN, F orCl.

Corresponding compounds according to the invention can be prepared byreplacing appropriate substituents or hydrogen atoms with the oxetanegroup of the formula (A).

F) The derivatives of quinaciridone consist of structural units of theformula (M)

where the benzo groups may each independently be substituted and whereat least one hydrogen atom is replaced by a substituent of the formula(A).

Similarly to R′ and R″, these substituents may be the same or differentand may each be a straight-chain, branched or cyclic alkyl or alkoxygroup having from 1 to 20 carbon atoms where one or more nonadjacent CH₂groups may be replaced by —O—, —S—, —CO—, —COO—, —O—CO—, —NR¹—,—(NR²R³)⁺—A⁻, or —CONR⁴—, and where one or more hydrogen atoms may bereplaced by F, or an aryl group having from 4 to 14 carbon atoms whichmay be substituted by one or more nonaromatic radicals R′. Furthermore,the substituents other than R′ and R″ may also be CN, F or Cl.

Corresponding compounds according to the invention can be prepared byreplacing appropriate substituents or hydrogen atoms with the oxetanegroup of the formula (A).

G) The organic lanthanide complexes consist of structural units of theformula (N)LnR′_(n)  (N)

The substituents R′ may be the same or different and each becarboxylates, ketonates, 1,3-diketonates, imides, amides or alkoxides,where at least one hydrogen atom is replaced by a substituent of theformula (A).

The number of ligands depends on the particular metal. Preference isgiven to the organic complexes of europium, gadolinium and terbium,particular preference to those of europium.

Corresponding compounds according to the invention can be prepared byreplacing appropriate substituents or hydrogen atoms in the substituentsby the oxetane group of the formula (A).

H) The derivatives of metal quinoxalinate consist of structural units ofthe formula (O)

where the benzo groups may each independently be substituted by radicalsR′, M is aluminum, zinc, gallium or indium, preferably aluminum; n is aninteger 0, 1, 2 or 3.

The substituents of the benzo group R′ may be the same or different andmay each be a straight-chain, branched or cyclic alkyl or alkoxy grouphaving from 1 to 20 carbon atoms where one or more nonadjacent CH₂groups may be replaced by —O—, —S—, —CO—, —COO—, —O—CO—, —NR¹—,—(NR²R³)⁺—A⁻, or —CONR⁴—, and where one or more hydrogen atoms may bereplaced by F, or an aryl group having from 4 to 14 carbon atoms whichmay be substituted by one or more nonaromatic radicals R′. Furthermore,the substituents other than R′ and R″ may also be CN, F or Cl. Theoxetane group according to the invention of the formula (A) may theneither replace a hydrogen atom on one of the quinoxaline rings, or elsebe on another ligand R′ which replaces one of the quinoxaline ligands.

I) The derivatives of oxadiazole consist of structural units of theformula (P)

where Ar′ and Ar″ may be the same or different and each be a substitutedor unsubstituted aromatic or heteroaromatic having from 4 to 14 carbonatoms, where at least one hydrogen atom is replaced by a substituent ofthe formula (A).

Preference is given to Ar′ and Ar″ being the same or different and eachbeing phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl, 2-, 3- or4-pyridinyl, 2-, 4- or 5-pyrimidinyl, 2-pyrazinyl, 3- or 4-pyridazinyl,2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline, 2- or 3-thiophenyl, 2- or3-pyrrolyl, 2- or 3-furanyl.

The possible substituents are the same or different and are each CN, F,Cl, CF₃ or a straight-chain, cyclic or branched alkyl or alkoxy grouphaving from 1 to 12 carbon atoms, where one or more nonadjacent CH₂groups may be replaced by —O—, —S—, —CO—, —COO—, —O—CO—, —NR¹—,—(NR²R³)⁺—A⁻—, or —CONR⁴—, and where one or more hydrogen atoms may bereplaced by F.

The oxetane group according to the invention of the formula (A) may theneither replace a hydrogen atom on one of the aryl rings, or else be onone of the substituents of the aryl rings.

J) Polymers (polystyrenes which bear tetraarylbenzidine units in theside chain consist of structural units of the formula (Q) or analogouscompounds in other basic polymer frameworks (polyacrylates, polyamides,polyesters)

where Ar′, Ar″, Ar′″ and Ar″″ may be the same or different and may eachbe a substituted or unsubstituted aromatic or heteroaromatic having from4 to 14 carbon atoms.

Preference is given to Ar′, Ar″, Ar′″ and Ar″″ being the same ordifferent and each being phenyl, 1- or 2-naphthyl, 1-, 2- or9-anthracenyl, 2-, 3- or 4-pyridinyl, 2-, 4- or 5-pyrimidinyl,2-pyrazinyl, 3- or 4-pyridazinyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinoline,2- or 3-thiophenyl, 2- or 3-pyrrolyl, 2- or 3-furanyl.

The possible substituents are the same or different and are each CN, F,Cl, CF₃ or a straight-chain, cyclic or branched alkyl or alkoxy grouphaving from 1 to 12 carbon atoms, where one or more nonadjacent CH₂groups may be replaced by —O—, —S—, —CO—, —COO—, —O—CO—, —NR¹—,—(NR²R³)⁺—A⁻, or —CONR⁴—, and where one or more hydrogen atoms may bereplaced by F.

This tetraarylbenzidine group is then bonded to the main polymer chainvia a spacer, preferably a C₁ to C₆ alkyl, alkoxy or ester group.

The oxetane group according to the invention of the formula (A) may theneither replace a hydrogen atom on one of the aryl rings, or be on one ofthe substituents of the aryl rings, or else on a further copolymerizedmonomer which bears no tetraarylbenzidine unit.

The above-outlined substances may be used in pure form or else in amixture with each other or with other auxiliaries.

The invention further provides mixtures or formulation comprising thematerials according to the invention and added auxiliaries, such asinitiators and optionally sensitizers, stabilizers, retarders,inhibitors, reactive diluents, etc.

At least one photoinitiator or a photoinitiator system is added to thematerials according to the invention. The concentration is typicallychosen within the range from 0.1 to 1.0% by weight, based on thecompound/polymer according to the invention. Irradiation with actinicradiation generates an acid which initiates a crosslinking reaction bycationic, ring-opening polymerization.

Structured irradiation allows a pattern of regions having crosslinkedmaterial and regions having uncrosslinked material to be obtained.Suitable operations (for example washing with suitable solvents) thenallows the regions having uncrosslinked material to be removed. Thisleads to the desired structuring.

When the crosslinking of relatively large areas is desired, crosslinkingmay be initiated after film formation by applying an acid.

A further advantageous effect according to the invention is that thecrosslinking increases the mechanical and thermal stability of thelayers generated with the materials according to the invention. Thisleads to the devices which comprise crosslinked materials according tothe invention having distinctly longer lives under correspondingconditions (for example thermal stress, mechanical stress). This effectis more marked the greater the degree of crosslinking.

This completes the subsequent application of the different layers aftercompleted crosslinking. For example, an already crosslinked layer may beeffected as a substrate for depositing further substances from theliquid phase. When the materials having different optical refractiveindices are selected in a targeted manner, the layer constructionobtained in this way may be used as a waveguide. Preference is given toapplying the emitter from the solution to an already crosslinked layerof a hole conductor or electron conductor. With the aid of the materialsaccording to the invention, it is possible to produce multilayer devicesusing soluble active materials.

The structuring is effected, as described above, by irradiation. This isa standard process in the present-day electronics industry and may beeffected, for example, by irradiating with lasers or by surfaceirradiation through an appropriate mask. In contrast to theabove-outlined mask with disadvantages, this mask harbors no risk ofdeposition, since there is in this case only radiation and no materialflow through the mask.

In the case of the laser as the source, lateral positioning is possibleeither by moving the substrate, the light source itself or by opticalaids. A possible aid for substrate movement is an XY-table which isdriven by stepping motors. Optical aids may be mirrors. Structuring isparticularly simple and rapid where a shadow mask is used which isirradiated with a surface light source, for example a very high pressureHg lamp.

The invention further provides the layers which result fromcrosslinking.

The invention therefore likewise provides a structured organicelectronic device which, for the purposes of this invention, has one ormore active layers, at least one of which has been produced from one ormore materials according to the invention of the formula (A).

The general construction of such devices has been described above, andis listed in detail here once again:

-   (i) OLEDs and PLEDs in analogy with EP 676 461 and WO 98-27136 and    the literature cited therein.-   (ii) Organic solar cells in analogy with WO 94-05045 and WO 98-48433    and the literature cited therein.-   (iii) Organic lasers in analogy with WO 98-03566 and the literature    cited therein.-   (iv) Organic circuits (ICs) in analogy with WO 95-31833 and WO    99-10939 and the literature cited therein.

The invention is further illustrated by the examples which follow,without wishing to restrict it.

Part A: Synthesis of the Monomers: Monomers for Units of the Formula (D)(Fluorenes)

Example M1 Preparation of9-(2,5-dimethylphenyl)-9-(4-oxymethylene{2-[(3-ethylyloxetane)-3-yl)}phenyl)-2,7-dibromofluorene(M1)

In a 50 ml four-neck flask, 808 mg (6 mmol) of2-ethyl-2-chloromethyloxetane (see Chemphyschem. 2000, 207), 345 mg (5.2mmol) of KOH (85%), 2.60 g (5 mmol) of9-(2,5-dimethylphenyl)-9-(4-hydroxyphenyl)-2,7-dibromofluorene (see WO00/22026) were cautiously admixed with KOH and heated to 150° C. Afurther three portions, each of 808 mg (each 6 mmol), of2-ethyl-2-chloromethyloxetane were then added over the course of twohours and the mixture was stirred at this temperature for a further 2hours. The reaction was followed by TLC (hexane/CHCl₃ 1:1). The reactionmixture was cooled and admixed at room temperature with 50 ml of water.The mixture was then admixed with ethyl acetate (50 ml). A white solidprecipitated which dissolved neither in the aqueous nor in the organicphase. It was filtered off with suction. After drying under reducedpressure, 2.2 g (3.55 mmol, 71%) of the monomer M1, which, according to¹H NMR, was >99% pure, were obtained. ¹H NMR (benzene-d₆, 400 MHz): 7.72(dd, 2H, J=2.0, 0.8, fluorene H1/H8); 7.28 (dd, 2H, J=2.0, 7.8, fluoreneH3/H6); 7.21 (br. s, 1H, H-6″ phenyl); 7.06 (d with fine structure, 4H,J=8.0 Hz, H-phenyl); 6.88-6.80 (m, 2H, H3″, H4″); 6.47 (d with finestructure, 2H, j, 7.7 Hz, fluorene H4/H5), 4.35 (d, J=7.2 Hz, 2Hoxetane); 4.25 (d, J=7.0 Hz, 2H-oxetane); 3.55 (s, 2H, OCH₂); 2.01 (s,3H, CH₃); 1.55 (q, 2H, J=6.8 Hz, CH₂-ethyl); including at 1.54 (s, 3H,CH₃); 0.61 (t, J=6.8 Hz, CH₃-ethyl).

Example M2 Preparation of9-(2,5-dimethylphenyl)-9-{6-[(3-methyloxetane)-3-yl)methoxy]-hexoxy}-2,7-dibromofluorene(Monomer M2)

In a similar manner to Example M1, 2.22 g (5 mmol) of9-(2,5-dimethylphenyl)-9-hydroxy-2,7-dibromofluorene (see WO 00/22026)were reacted with 2.65 g (2 eq) of(6′-bromohexyloxy-3-methyl)-3-methyloxetane (see Polym. J. 1993; 25,1283) at 50° C. for 23 h. 2.04 g (3.25 mmol, 65%) of the monomer M2 wereobtained which, according to ¹H NMR, was of >98% purity.

¹H NMR (CDCl₃, 400 MHz): 7.50 2 (br. s, 7H, fluorene-H, H6); 7.06 (d,1H, J=8.0 Hz, H-3′); 6.88 (d, 1H, J=8.0 Hz, H-4′); 4.38 (d, J=7.2 Hz, 2Hoxetane); 4.22 (d, J=7.0 Hz, 2H oxetane); 3.63 (m, 4H, OCH₂); 2.88 (s,2H, OCH₂); 2.31 (s, 3H, CH₃); 1.78-1.20 (m, 14H, 4×CH₂, 2×CH₃).

Example M3 Preparation of9,9-bis{6-[(3-methyloxetane)-3-yl)methoxy]-hexoxy}-2,7-dibromofluorene(M3)

In a 250 mL one-neck flask equipped with a reflux condenser, 1.44 g (60mmol) of NaH were suspended in 50 mL of dry toluene and 50 mL of dryDMA. 3.24 g (10 mmol) of 2,7-dibromofluorene and 5.57 g (21 mmol) of(6′-bromohexyloxy-3-methyl)-3-methyloxetane were added to this reactionmixture and heated to 100° C. for 1 h. After cooling to roomtemperature, 1 mL of H₂O was cautiously added by pipette and then 150 mLof Et₂O were added. The organic phase was washed with 4×50 mL of H₂O,then dried over MgSO₄ and the solvents were removed in vacuo. The pureproduct was obtained by column chromatography (twice) on silica gelusing an eluent mixture of ethyl acetate:petroleum ether=1:2. Yield:3.78 g (39%) of viscous oil.

¹H NMR (CDCl₃, 300 MHz): 0.65 (m, 4H), 1.09 (m, 4H), 1.27 (s, 6H), 1.40(m, 4H), 1.89 (m, 4H), 3.34 (t, J=6.6 Hz, 4H), 3.40 (s, 4H), 4.31-4.47(AA′BB′ system, J=5.7 Hz, 8H), 7.43-7.51 (AA′BB′ system, J=8.1 Hz, 4H),7.43 (m, 2H). ¹³C NMR (CDCl3, 75 MHz): δ=21.4 (CH3), 24.0 (CH2), 26.1(CH2), 29.8 (CH2), 30.0 (CH2), 40.3 (C_(quart)) 40.5 (CH2), 56.0(C_(quart)), 71.9 (CH₂), 76.4 (CH₂), 80.6 (CH2), 121.6 (CH), 121.9 (CH),126.5 (CH), 130.6 (C_(quart)), 139.5 (C_(quart)), 152.8 (C_(quart)). MS(70 eV, 70 eV, m/z (%)): 692 (M+, 100), 690 (50), 662 (12), 614 (12),612(11), 349 (14), 323 (30), 245 (10), 243 (10), 85 (38), 55 (23). IR(film, KBr):=3048 cm⁻¹, 2931, 2860, 2797, 1598, 1570, 1450, 1416, 1398,1378, 1264, 1117, 1061, 1004, 979, 940, 878, 835, 811, 741 666, 427.UV/vis (CHCl₃) λ_(max) (ε)=282 nm (26178), 303 nm (14170), 314 nm(10110). C₃₅II₄₈Br₂O₄ (092.58): calc., C, 80.70; H, 8.99; Br, 23.07.found: C, 61.24; H, 6.83; Br, 22.77.

Example M4 Preparation of Monomer M4 (see Scheme 1)

M4 was prepared in a similar manner to M1 using 2.2 eq of(6′-bromohexyloxy-3-methyl)-3-methyloxetane. After a similar workup, 56%of M4 were obtained as a colorless solid.

The structures of the monomers according to the invention M1-M4 used andof further monomers are summarized in Scheme 1:

Part B: Preparation of the Polymers

Example P1

Copolymerization of monomer M1,2,7-dibromo-9-(2′,5′-dimethyl-phenyl)-9-[3″,4″-bis(2-methylbutyloxy)phenyl]fluorene(M9), N,N′-bis(4-bromo-phenyl)-N,N′-bisphenylbenzidine (M10) andpinacolyl9-(3,7-dimethyloctyloxyphenyl)-9-(2,5-dimethylphenyl)fluorene-2,7-bisborate(M8) by Suzuki reaction (polymer P1). 1.6237 g (2.400 mmol) of2,7-dibromo-9-(2′,5′-dimethyl-phenyl)-9-[3″,4″-bis(2-methylbutyloxy)phenyl]fluorene(M9), 4.5281 g (6.00 mmol) of pinacoyl9-(3,7-dimethyloctyloxyphenyl)-9-(2,5-dimethylphenyl)fluorene-2,7-bisborate(M8), 0.7757 g (1.200 mmol) ofN,N′-bis(4-bromophenyl)-N,N′-bis(phenyl)benzidine (M10), 1.4842 g (2.400mmol) of monomer M1, 5.80 g (25.2 mmol) of K₃PO₄.H₂O, 18 ml of toluene,9 ml of water and 0.15 ml of ethanol were degassed by passing N₂ throughfor 30 min. 57 mg (0.05 mmol) of Pd(PPh₃)₄ were then added underprotective gas. The suspension was stirred vigorously under an N₂blanket at an internal temperature of 87° C. (gentle reflux). After 4days, a further 0.10 g of pinacoyl9-(3,7-dimethyloctyloxyphenyl)-9-(2,5-dimethylphenyl)fluorene-2,7-bisboratewas added. After heating for a further 6 hours, 0.3 ml of bromobenzenewas added and heated was continued to a reflux for a further 3 h.

The reaction solution was diluted with 200 ml of toluene, and thesolution was extracted by stirring with 200 ml of 2% aqueous NaCN for 3h. The mixture lightened almost completely. The organic phase was washedwith H₂O and precipitated by adding to 800 ml of ethanol. The polymerwas dissolved in 200 ml of chloroform at 40° C. for 1 h, filteredthrough Celite and precipitated with 250 ml of MeOH, washed and driedunder reduced pressure. Precipitation was effected once more in 200 mlof THF/250 ml of methanol, followed by filtration with suction anddrying to constant mass. 4.80 g (9.64 mmol, 80%) of the polymer P1 wereobtained as a slightly yellow solid.

¹H NMR (CDCl₃): 7.9-6.6 (m, fluorene-H, phenyl-H); 4.52 and 4.43 (2×d,J˜8 Hz, each 0.4H, oxetane H); 4.0-3.4 (3×m, OCH₂), 2.20 (s, CH₂-ethyl,arom-CH₃); 1.9-0.7 (m, alkyl H).

GPC: THF; 1 ml/min, PLgel 10 μm Mixed-B 2×300×7.5 mm², 35° C., RIdetection: Mw=77000 g/mol, Mn=32000 g/mol.

Further polymers were prepared in a similar manner to the descriptionsfor P1. The chemical properties are summarized in the table whichfollows. Some comparative polymers without oxetane units were alsoprepared. These are also listed in the table. All of these polymers werealso investigated for use in PLEDs. The preparation of PLEDs is firstlydetailed above and is described in more detail in Part C. The mostimportant device properties (color, efficiency) are also listed in thetable. In the case of the polymers P1-P9, the chemical andelectrooptical data of the uncrosslinked polymers are shown. Thecrosslinking is likewise described in Part C.

TABLE 1 Important characteristic data of the polymers investigated GPC*Electroluminescence** Proportion of the monomers in the M_(W) M_(N)Voltage at Polymer polymerization [%] (·1000 (·1000 λ_(max) Max. Eff.100 Cd/m² (type)* Monom. 1 Monom. 2 Monom. 3 Monom. 4 g/mol) g/mol) [nm][Cd/A] [V] P1 20% M1 20% M9 10% M10 50% M8 77 32 468 1.1 7.5 P2 25% M225% M5 50% M6 56 29 476 1.0 7.9 P3 25% M3 25% M5 50% M6 43 18 478 1.27.2 P4 25% M4 25% M5 50% M6 65 33 476 1.1 7.0 P5 25% M4 15% M9 10% M1050% M7 124 51 468 2.1 5.5 P6 25% M2 15% M9 10% M10 50% M7 134 54 466 2.25.4 P7 50% M1 50% M6 79 38 477 1.0 7.1 P8 50% M4 40% M7 10% M9 73 34 4671.9 5.3 P9 30% M2 10% M11 10% M10 50% M8 81 38 550 6.5 4.9 C1 40% M9 10%M10 50% M8 79 33 469 1.1 7.8 C2 50% M5 50% M6 49 22 478 0.9 8.2 C3 40%M9 10% M10 50% M7 141 65 466 2.2 5.3 *GPC measurements THF; 1 ml/min,Plgel 10 μm Mixed-B 2 × 300 × 7.5 mm², 35° C., RI detection wascalibrated against polystyrene **For production of the polymer LEDs, seePart C

Part C: Production and Characterization of LEDs, Crosslinking of thePolymers According to the Invention

The LEDs were produced by the general procedure outlined hereinbelow.This of course had to be adapted ad hoc to the particular circumstances(for example polymer viscosity and optimal layer thickness of thepolymer in the device). The LEDs described hereinbelow were eachtwo-layer systems, i.e. substrate//ITO//PEDOT//polymer//cathode.

PEDOT is a polythiophene derivative.

General Procedure for Producing High-Efficiency, Long-Life LEDs:

Once the ITO-coated substrates (for example glass support, PET film)have been cut to the correct size, they are cleaned in a plurality ofcleaning steps in an ultrasound bath (for example soap solution,Millipore water, isopropanol).

For drying, they are blown with an N₂ gun and stored in a desiccator.Before coating with the polymer, they are treated with an ozone plasmaunit for approx. 20 minutes. A solution of the respective polymer(generally having a concentration of 4-25 mg/ml in, for example,toluene, chlorobenzene, xylene:cyclohexanone (4:1)) is prepared anddissolved by stirring at room temperature. Depending on the polymer, itmay also be advantageous to stir at 50-70° C. for some time. When thepolymer has dissolved completely, it is filtered through a 5 μm filterand coated using a spin coater at variable speeds (400-6000). Thisallows the layer thicknesses to be varied within the range from approx.50 to 300 nm. A conductive polymer, preferably doped PEDOT or PANI, isusually applied initially to the (structured) ITO.

Electrodes are also applied to the polymer films. This is generallyeffected by thermal evaporation (Balzer BA360 or Pfeiffer PL S 500). Thetransparent ITO electrode is then connected as the anode and the metalelectrode (for example Ba, Yb, Ca) as the cathode, and the deviceparameters are determined.

The results obtained with the polymers described are summarized in thetable in Part B.

Crosslinking

The crosslinking of the polymers according to the invention was achievedby the following procedure:

The polymers were admixed in toluene solution (1.5%) with 3% by weight(based on the polymer) of photoacid(4-(thiophenoxyphenyl)diphenylsulfonium hexafluoro-antimonate) and spincoated under N₂ as described above. After drying the film, crosslinkingwas effected by irradiation using a UV lamp (10 W, 302 nm, 5 min). Thefilm was then heat treated at 200° C. for 3 minutes under N₂ (ExampleP1, 130° C. for Examples P2-P9) and then treated with a 10⁻⁴ molarLiAlH₄ solution in THF. The device data for crosslinked anduncrosslinked polymer P1 are illustrated in FIG. 1. The values shownthere were not obtained under optimized conditions (cathode/devicestructure), so that the absolute values of the efficiencies are lowerthan in Table 1.

Proof of Crosslinkability and Photostructurability

A thin film of thickness 50 nm was produced from the polymer P5 admixedwith photoacid (see above) and illuminated through a comb structurehaving 200 μm teeth for 20 sec. The film was heated at 120° C. for 20seconds and the soluble part was then washed off with THF. The profileobtained using a profilometer (FIG. 2) shows good agreement with theilluminated structure.

1. A low molecular weight or polymeric organic electroluminescent orlaser material for use in electronic applications selected from thegroup consisting of A) a homo- or copolymer based on polyspiro, B) a lowmolecular weight compound having a 3-dimensional spirobifluorenestructure, C) a low molecular weight compound having a 3-dimensionaltriptycene structure, and D) a derivative of quinacridone having atleast one hydrogen atom, wherein at least one hydrogen atom is replacedby a group of the formula (A)

wherein R is a straight-chain, branched or cyclic alkyl, alkoxyalkyl,alkoxy, thioalkoxy group having from 1 to 20 carbon atoms, C₄-C₁₈-arylor C₂-C₁₀-alkenyl, in each of which one or more hydrogen atoms isoptionally replaced by halogen or CN, and one or more nonadjacent carbonatoms is optionally replaced by —O—, —S—, —CO—, —COO— or —O—CO—, Z is—O—, —S—, —CO—, —COO—, —O—CO— or a bivalent group —(CR₁R₂)_(n)— in whichR₁ and R₂ are each independently hydrogen, a straight-chain, branched orcyclic alkyl, alkoxy, alkoxyalkyl, thioalkoxy group having from 1 to 20carbon atoms, C₄-C₁₈-aryl or C₂-C₁₀-alkenyl, in each of which one ormore hydrogen atoms is optionally replaced by halogen or CN, and one ormore nonadjacent carbon atoms is optionally replaced by —O—, —S—, —CO—,—COO— or —O—CO—, X is —O— or a bivalent group —(CR₁R₂)_(n)— in which R₁and R₂ are each independently hydrogen, a straight-chain, branched orcyclic alkyl, alkoxy, alkoxyalkyl, thioalkoxy group having from 1 to 20carbon atoms, C₄-C₁₃-aryl or C₂-C₁₀-alkenyl, in each of which one ormore hydrogen atoms is optionally replaced by halogen or CN, and n is aninteger from 1 to 20, with the proviso that the number of these A groupsis limited by the maximum number of available substitutable hydrogenatoms.
 2. The material as claimed in claim 1, wherein said halogen inthe definition of R, X and Z is Cl or F and n is an integer from 3 to10.
 3. The material as claimed in claim 2, wherein n is an integer from3 to
 6. 4. The material as claimed in claim 1, wherein the content ofoxetane group according to formula (A) by the molar ratio of oxetanerings, based on all organic rings including the oxetane rings in theparticular structure, is from 0.01 to 0.6.
 5. A low molecular weight orpolymeric organic electroluminescent or laser material for use inelectronic applications selected from the group consisting of A) a homo-or copolymer based on poly(p-phenylene-vinylene) (“PPV”) or polyspiro,B) a low molecular weight compound having a 3-dimensionalspirobifluorene structure, C) a low molecular weight compound having a3-dimensional triptycene structure, and D) a derivative of quinacridonewherein each material contains at least one cross-linking enabledoxetane group.
 6. The material as claimed in claim 5, wherein thecontent of oxetane group by the molar ratio of oxetane rings, based onall organic rings including the oxetane rings in the particularstructure, is from 0.01 to 0.6.
 7. The material as claimed in claim 1,wherein X is —O— or a bivalent group —(CR₁R₂)_(n)— in which R₁ and R₂are each independently hydrogen, a straight-chain, branched or cyclicalkyl, alkoxy, alkoxyalkyl, thioalkoxy group having from 1 to 20 carbonatoms C₄-C₁₈-aryl or C₂-C₁₀-alkenyl, in each of which one or morehydrogen atoms is optionally replaced by Cl, F or CN.
 8. The material asclaimed in claim 5, wherein said material is a homo- or copolymer basedon PPV.
 9. The material as claimed in claim 1, wherein said material isa homo- or copolymer based on polyspiro containing at least one group ofthe formula (A).
 10. The material as claimed in claim 5, wherein saidmaterial is a homo- or copolymer based on polyspiro.
 11. The material asclaimed in claim 1, wherein said material is a low molecular weightcompound having a 3-dimensional spirobifluorene structure containing atleast one group of the formula (A).
 12. The material as claimed in claim5, wherein said material is a low molecular weight compound having a3-dimensional spirobifluorene structure.
 13. The material as claimed inclaim 1, wherein said material is a low molecular weight compound havinga 3-dimensional triptycene structure.
 14. The material as claimed inclaim 5, wherein said material is a low molecular weight compound havinga 3-dimensional triptycene structure.
 15. The material as claimed inclaim 1, wherein said material is a derivative of quinacridone.
 16. Thematerial as claimed in claim 5, wherein said material is a derivative ofquinacridone.